U.S. Pat. No. 4,476,184, disclosed thermoplastic polysulfone oligomers having dimethyloxynadic (DONA) crosslinkable end caps to impart solvent-resistance to the cured resins. Similar oligomers having difunctional nadic, maleic, and phenylacetyleneic end caps are disclosed in U.S. Pat. No. 4,536,559.
Recently, chemists have sought to synthesize oligomers for high performance advanced composites suitable for aerospace applications. These composites should exhibit solvent resistance (particularly to MEK and methylene chloride); be tough, impact resistance, and strong; be easy to process; and be thermoplastic. Oligomers and composites that have thermo-oxidative stability and, accordingly, can be used at elevated temperatures are particularly desirable.
While epoxy-based composites are suitable for many applications, their brittle nature and susceptibility to thermal and hydrolytic degradation make then inadequate for many aerospace applications, especially those applications which require thermally stable, tough composites or service in harsh conditions. Accordingly, research has recently focused on polyimide composites to achieve an acceptable balance between thermal or hydrolytic stability, solvent resistance, and toughness, Still the maximum temperatures for use of the polyimide composites, such as PMR-15, are about 600.degree.-625.degree. F., since they have glass transition temperature of about 690.degree. F. PMR-15 also suffers from brittleness.
There has been a progression of polyimide sulfone compounds synthesized to provide unique properties or combinations of properties. For example, Kwiatkowski and Brode synthesized maleic-capped linear polyacrylimides as disclosed in U.S. Pat. No. 3,839,287. Holub and Evan synthesized maleic- or nadic-capped, imido-substituted polyester compositions as disclosed in U.S. Pat. No. 3,729,446. We synthesized thermally stable polysulfone oligomers as disclosed in U.S. Pat. No. 4,476,184 or U.S. Pat. No. 4,536,559, and have continued to make advances with polyetherimidesulfones, polybenzoxazolesulfoens, plybutadienesulfones, and "star" or "star-burst" multidimensional oligomers. We have shown surprisingly high glass transition temperatures yet reasonable processing and desirable physical properties in many of these oligomers and their composites.
Polybenzoxazoles, such as those disclosed in our U.S. Pat. Nos. 4,965,336 and 4,868,270 may be used at temperatures up to about 750.degree.-775.degree. F., since these composites have glass transition temperatures of about 840.degree. F. Some aerospace applications need composites which have even higher use temperatures while maintaining toughness, solvent resistance, ease of processing, formability, strength, and impact resistance.
Multidimensional oligomers, such as disclosed in our U.S. Pat. No. 5,210,213 are easier to process than some advanced composite oligomers since they can be handled at lower temperatures. Upon curing, however, the oligomers chemically crosslink through their end caps in addition polymerization so that the thermal resistance of the resulting composite is markedly increased with only a minor loss of stiffness, matrix stress transfer (impact resistance), toughness, elasticity, and other mechanical properties. Glass transition temperatures above 950.degree. F. are achievable.
Commercial polyesters, when combined with well-known diluents, such as styrene, do not exhibit satisfactory thermal and oxidative resistance to be useful for aircraft or aerospace applications. Polyarylesters (i.e., arylates) are often unsatisfactory, also, since the resins often are semi-crystalline which may makes them insoluble in laminating solvents, intractable in fusion, and subject to shrinking or warping during composite fabrication. Those polyarylesters that are soluble in conventional laminating solvents remain so in composite form, thereby limiting their usefulness in structural composites. The high concentration of ester groups contributes to resin strength and tenacity, but also makes the resin susceptible to the damaging effects of water absorption. High moisture absorption by commercial polyesters can lead to distortion of the composite when it is loaded at elevated temperature.
High performance, aerospace, polyester advanced composites, however, can be prepared using crosslinkable, and capped polyester imide ether sulfone oligomers that have an acceptable combination of solvent resistance, toughness, impact resistance, strength, ease of processing, formability, and thermal resistance. By including Schiff base (--CH.dbd.N--), imidazole, thiazole, or oxazole linkages in the oligomer chain, the linear, advanced composites formed with polyester oligomers of our copending application U.S. Ser. No. 726,259 can have semiconductive or conductive properties when appropriately doped.
Conductive and semiconductive plastics have been extensively studies (see, e.g., U.S. Pat. Nos. 4,375,427; 4,338,222; 3,966,987; 4,344,869; and 4,344,870), but these polymers do not possess the blend of properties which are essential for aerospace applications. That is, the conductive polymers do not possess the blend of (1) toughness, (2) stiffness, (3) elasticity, (4) case of processing, (5) impact resistance (and other matrix stress transfer capabilities), (6) retention of properties over a broad range of temperatures, and (7) high temperature resistance that is desirable on aerospace advanced composites. The prior art composites are often too brittle.
Thermally stable multidimensional oligomers having semiconductive or conductive properties when doped with suitable dopants are also known and are described in our copending applications (including U.S. Ser. No. 773,381 to Lubowitz, Sheppard, and Torre), The linear arms of the oligomers contain conductive linkages, such as Schiff base (--N.dbd.CH--) linkages, between aromatic groups. Sulfone and either linkages are interspersed in the arms. Each arm is terminated with a mono- or difunctional end cap (i.e. an end cap having one or two crosslinking functionalities) to allow controlled crosslinking upon heat-induced or chemically-induced curing. Other "semiconductive" oligomers are described in our other copending applications.
Polyamide oligomers and blends are described in our U.S. Pat. Nos. 4,936,523, 4,847,333, and 4,876,328 and polyetherimide oligomers and blends are described in our U.S. Pat. No. 4,851,495.
Polyamideimides are generally injection-moldable, amorphous, engineering thermoplastics which absorb water (swell) when subjected to humid environments of immersed in water. Polyamideimides are generally described in the following patents: U.S. Pat. Nos. 3,658,938; U.S. Pat. Nos. 4,628,079; 4,599,383; 4,374,144; or 3,988,344. The thermal integrity and solvent-resistance can be greatly enhanced by capping amideimide backbones with monomers that present one or two crosslinking functionalities at each end of the oligomer, as described in our copending applications U.S. Ser. No. 092,740 and 181,013.
Blends of these oligomers comprise a mixture of an oligomer and a compatible polymer, generally of the same chemical family and of substantially the same backbone. The polymer is formed by an analogous condensation generally substituting a noncrosslinking end-cap monomer (such as phenol, benzoic acid chloride, or aniline) for the crosslinking end cap used in the oligomers. Advanced composite (mixed chemical) blends and coreactive blends have also been described in our copending applications Ser. No. 167,604 and 174,747, respectively.
Interpenetrating or semi-interpenetrating networks are also known, such as those described by Egli Et al. in "Semi-Interpenetrating Networks of LARC-TPI" available from NASA-Langley Research Center.
The ethersulfone oligomers, blends, prepregs, and composites of the present invention provide aromatic ethersulfone materials which an improved mixture of properties over their prior art competitors, including solvent resistance and thermal stability. They are useful in many aerospace applications unsuited for their prior art materials.